Patent GB-692332-A (GB)
Title: Improvements relating to quaternary ammonium compounds, and their uses
IPC: C07C237/00
Filed: 1951-07-17
Abstract: The invention comprises quaternary ammonium compounds of the formula <FORM:0692332/IV (b)/1> where A1 and A2 are benzene or naphthalene residues free from salt-forming substituents, R is hydrogen, methyl or ethyl, Z is a divalent aliphatic residue attached to the quaternary nitrogen atom by a carbon atom and n and m are 1 or 2. The compounds are made by reacting 1 or 2 mols. of dimethylamine in any order with 1 mol. of A1-(Z-Hal)n and 1 or 2 mols. of A2-NH-CO-CHR-Hal; other salts may be made by forming the quaternary hydroxide by the action of alkali hydroxide or carbonate and treating this with the appropriate acid (e.g. orthophosphoric, perchloric, hydrofluosilicic, lactic, citric, tartaric or salicylic).  One or both of the nuclei A1 and A2 must contain a trifluoromethyl group. The reaction may take place at 70-130 DEG  C. under normal or increased pressure in an inert solvent, preferably ethyl acetate or toluene.  Examples show the production of compounds where n is 1, R is hydrogen and ethyl, A1 is m-trifluoromethylphenyl, 2 : 4- and 3 : 4-dichlorophenyl, A2 is m-trifluoromethylphenyl, 2- and 4-chloro-3-trifluoromethylphenyl, and Z is -CH2-, -CH2CO-, -CH2CH2O-, -CH2CONH-, -CH2CON(CH3)- and -CH2CH2OCONH-; also where n is 2, R is hydrogen, A1 is p-phenylene and p-xylylene, A2 is 4-chloro-3-trifluoromethylphenyl and Z is -CH2-, -CH2CH2O- and -CH2CONH-.  A list is given of further compounds where n is 1, A1 is a benzene or naphthalene nucleus carrying as substituents methyl, t.-amyl, methoxy, phenoxy, p - chlorophenoxy, p - tolyloxy, chlorine, bromine, iodine or nitro, A2 is m-trifluoromethylphenyl, optionally substituted by chlorine or by p-chloro-phenoxy, R is hydrogen or ethyl and Z is -CH2-, -CH2CO-, -CH2CH2O-, -CH2CONH-, -CH(C2H)-CO-NH-, -CH2-CO-N(CH3)- or -CH2 CH2OCH2CH2O-; also where n is 2, A1 is p-phenylene, p-xylylene, naphthylene, pp1-diphenyl or pp1-thiodiphenyl, A2 is m-trifluoromethylphenyl optionally substituted by chlorine and Z is -CH2-, -CH2CH2O- or -CH2 CONH-. Other possible groups are mentioned.  The quaternary salts described are all chlorides or bromides.  Intermediates of the formula A2-NH-CO-CHR-N(CH3)2 are prepared by reacting the corresponding halogen compounds with dimethylamine. There are thus prepared dimethylaminoacetyl-m-trifluoromethyl - anilide.  a  - dimethylaminobutyryl - m - trifluoromethyl - anilide, dimethylaminoacetyl - 4 - chloro - 3 - trifluoromethyl - anilide, dimethylaminoacetyl - 3 : 4 - dichloranilide, dimethylaminoacetyl - N - methyl - 3 : 4 - dichloranilide and N : N1 - bis - (dimethylaminoacetyl)-p-phenylene diamine.  Intermediates of the formula A2-NH-CO-CHR-Hal are made by reacting aromatic primary amines with reactive derivatives (e.g. chlorides) of a -halofatty acids. There are thus made chloracetyl - m - trifluoromethyl - anilide, chloracetyl - 3 : 4 - dichloranilide, a  - chlorobutyryl - m - trifluoromethyl - anilide, chloracetyl - 4 - chloro - 3 - trifluoromethyl - anilide, chloracetyl - 2 - chloro - 5 - trifluoromethyl - anilide, chloracetyl - N - methyl - 3 : 4 - dichloranilide and N : N1 - bis - (chloracetyl) - p - phenylene diamine.  Intermediates of the formula A1-Z-N(CH3)2 are obtained by reacting the corresponding halogen compounds with dimethylamine; so prepared are 2 : 4-dichlorphenol b -dimethylaminoethyl ether and hydroquinone bis-(b -dimethylaminoethyl ether).  Intermediates of the formula A1-Z-Hal are prepared by (1) reacting phenols or naphthols with alkylene chlorhydrins and treating the products with thionyl chloride; (2) treating 1 mol. of a phenol or naphthol with 1 mol. of b b 1-dichlorodiethyl ether; (3) reacting phenols or naphthols with b -chloroethyl chloroformate; or (4) treating aryl isocyanates with alkylene chlorhydrins.  Various monohydric and dihydric phenols and naphthols are specified, including pp1 - dihydroxydiphenyl sulphone. 2 : 4-Dichlorphenol b -chloroethyl ether and hydroquinone bis-(b -chloroethyl ether) are made by method (1), the corresponding b -hydroxyethyl ethers being formed intermediately.  3 : 4 - Dichlorphenylcarbamic b  - dimethylaminoethyl ester is obtained from 3 : 4-dichlorphenyl isocyanate and b  - dimethylaminoethanol.  3 : 4 - Dichloro - N - methylaniline is prepared from 3 : 4-dichloraniline by conversion into the N - p - toluenesulphonyl derivative, methylation with dimethyl sulphate and hydrolysis.  Specification 513,663 is referred to.